CN115772548B - Method for joint production of organic acid and L-lysine - Google Patents
Method for joint production of organic acid and L-lysine Download PDFInfo
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Abstract
The invention discloses a method for jointly producing organic acid and L-lysine, which belongs to the technical field of organic acid, and comprises the following steps: l-lysine production and organic acid production; evaporating and deaminizing the dissociation collection liquid in the ion exchange generated in the production of the L-lysine, and concentrating and deaminizing the dissociation collection liquid in the ion exchange to obtain ammonia water with the mass fraction of 3-5% for adjusting the pH value by organic acid fermentation; the nitrogen source in the production of the L-lysine is ammonium salt generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of organic acid, and the carbon source is glucose. The invention can improve the utilization rate of ammonia, realize the closed-loop production of the organic acid and the L-lysine, reduce the energy consumption of raw materials, water, electricity and the like, reduce the production cost of the organic acid and the L-lysine, and improve the yield and the quality of the organic acid and the L-lysine.
Description
Technical Field
The invention relates to the technical field of organic acid, in particular to a method for jointly producing organic acid and L-lysine.
Background
L-lysine is basic essential amino acid, which is one of essential amino acids for human and mammal, and the organism can not synthesize itself, and must be supplemented from food, mainly in animal food and beans, and the content of lysine in cereal food is very low. The L-lysine has positive nutritional significance in the aspects of promoting the growth and development of human bodies, enhancing the immunity of organisms, resisting viruses, promoting fat oxidation, relieving anxiety and emotion and the like, can promote the absorption of certain nutrients, can cooperate with the nutrients, and can better exert the physiological functions of various nutrients.
At present, the production of L-lysine is mainly carried out by a fermentation method, the L-lysine is adsorbed and desorbed by adopting cation exchange resin, the pH of the material is regulated by sulfuric acid in the ion exchange process, and ammonia water is used for eluting, but excessive ammonia water is adopted in the eluting process, and the ammonia water is difficult to purify due to impurities carried by the ammonia water after eluting, difficult to recycle or is used as sewage to be discharged and treated, so that the sewage treatment cost is greatly increased, and waste is caused.
Organic acids refer to some organic compounds with acidity, including natural organic acids and synthetic organic acids; the natural organic acid is mainly extracted and separated from plants or agricultural and sideline products in the nature to obtain the organic acid with certain physiological activity, and the synthetic organic acid is obtained by a chemical synthesis method, an enzyme catalysis method and a microbial fermentation method.
At present, the most commonly used synthetic organic acid method is a microbial fermentation method, fermentation broth is obtained after microbial fermentation, then the fermentation broth is extracted by an ion exchange extraction method, a large amount of ammonia water is needed for neutralizing the fermentation broth in the fermentation process, a large amount of hydrochloric acid or sulfuric acid is adopted in the elution process, a large amount of by-product ammonium chloride or ammonium sulfate is produced, and the treatment is difficult.
The L-lysine and the organic acid are co-produced, so that the problems in the respective production can be fully solved, ammonia water generated after lysine elution is concentrated and recycled to the organic acid fermentation for the use of the organic acid fermentation to adjust the PH, and a large amount of ammonia water generated in the L-lysine production process is recovered; the ammonium chloride generated after the organic acid ion exchange elution is recycled to the L-lysine ion exchange elution process, the ammonia consumption of the lysine ion exchange process and the consumption of the concentrated L-lysine acid-regulating crystalline chloride ions are supplemented, and the ammonium sulfate is used as a nitrogen source for L-lysine fermentation, so that the utilization rate of ammonia is improved; realizes the joint production of the organic acid and the lysine, does not produce solid calcium sulfate waste residue in the production process of the organic acid, reduces the production cost and improves the utilization rate of raw materials.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for jointly producing organic acid and L-lysine, which can improve the utilization rate of ammonia, realize closed-loop production of the organic acid and the L-lysine, reduce the energy consumption of raw materials, hydropower and the like, and improve the yield and quality of the organic acid and the L-lysine.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for jointly producing organic acid and L-lysine comprises the following steps: l-lysine production and organic acid production;
the organic acid is one of succinic acid, tartaric acid, citric acid and itaconic acid;
the method comprises the steps of L-lysine production, adding a culture medium into a fermentation tank, sterilizing the culture medium, regulating the pH of the culture medium to 6.5-7.5 by using ammonia water, keeping the pH constant, inoculating corynebacterium glutamicum seed liquid into the culture medium according to the proportion of 10-20%, introducing sterile air according to the volume ratio of ventilation quantity to the culture medium of 0.3:1, controlling the tank pressure of the fermentation tank to be 0.1-0.2MPa in the fermentation process, feeding a carbon source and a nitrogen source, using ammonium chloride or ammonium sulfate as the nitrogen source, culturing for 30-48h, regulating the pH to 2.5-4.5 by using sulfuric acid, filtering by using a subsequent membrane, carrying out ion exchange, concentrating, crystallizing to obtain pure L-lysine and L-lysine crystallization mother liquor, recycling the L-lysine crystallization mother liquor in the production system, evaporating and deaminizing the solution in the ion exchange generated in the production of L-lysine, and concentrating and deaminizing the solution in the ion exchange solution for regulating the pH by using the ammonia water for organic acid fermentation;
The initial concentrations of the components of the culture medium in the L-lysine production are respectively as follows: glucose 50-52g/L KH 2 PO 4 1-1.2g/L，MgSO 4 •7H 2 0 0.25-0.3g/L，（NH 4 ） 2 S0 4 40-43g/L，MnSO 4 0.05-0.06g/L，FeSO 4 0.05-0.07g/L，ZnC1 2 1-1.3mg/L，CuS0 4 0.2-0.3mg/L, biotin 100-130ug/L, vitamin B1 200-220 ug/L;
the nitrogen source in the production of the L-lysine is ammonium sulfate or ammonium chloride generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of organic acid, and the carbon source is glucose.
The organic acid production consists of the following steps: fermenting organic acid, filtering by a ceramic membrane, nanofiltration, adsorbing cations, adsorbing anions, concentrating and refining in vacuum, and treating waste liquid generated in the production of the organic acid;
the pH value of the organic acid fermentation is controlled to be 6.5-7.5 by adding ammonia water in a flowing way in the fermentation process of the organic acid, and the organic acid ammonium pretreatment liquid is obtained after the fermentation is finished;
in the organic acid fermentation, the preparation method of the ammonia water comprises the steps of adding liquid ammonia into the ammonia water obtained in the L-lysine production to adjust the concentration of the ammonia water to 5-20%;
the ceramic membrane is used for filtering, the organic acid ammonium pretreatment liquid is introduced into a modified 50-100nm ceramic membrane for filtering, and the organic acid ammonium clear liquid is obtained after the filtering is finished;
in the ceramic membrane filtration, the temperature is 75-80 ℃, the flow rate is 0.3-0.5m/s, and the pressure is 4-5KPa during the filtration;
The preparation method of the modified 50-100nm ceramic film comprises the following steps: placing a silicon nitride ceramic film with the thickness of 50-100nm into a primary activating solution for primary soaking, controlling the temperature at 85-90 ℃ for 1-1.2h during primary soaking, and obtaining a ceramic film after primary soaking after the primary soaking is finished; placing the ceramic membrane after primary soaking in secondary activating solution for secondary soaking, controlling the temperature at 65-70 ℃ for 50-55min when the secondary soaking is finished, obtaining the ceramic membrane after secondary soaking, placing the ceramic membrane after secondary soaking in ammonia water for tertiary soaking, controlling the temperature at-25 ℃ to-20 ℃ when the tertiary soaking is finished, and controlling the time at 25-30min, placing the ceramic membrane in a sintering furnace after the tertiary soaking is finished, heating to 550-580 ℃ at the heating rate of 2-2.5 ℃/min, sintering for 1-1.2h at 550-580 ℃, and naturally recovering to room temperature to obtain the modified ceramic membrane with the wavelength of 50-100 nm;
in the preparation of the modified 50-100nm ceramic film, the weight ratio of the 50-100nm silicon nitride ceramic film to the primary activating solution is 1:3.5-4;
in the preparation of the modified 50-100nm ceramic membrane, the primary activating solution comprises the following components in parts by weight: 8-10 parts of sodium hydroxide, 2-3 parts of aluminum sulfate, 1-1.5 parts of potassium sodium tartrate and 90-95 parts of deionized water;
In the preparation of the modified 50-100nm ceramic membrane, the weight ratio of the ceramic membrane after primary soaking to the secondary activating solution is 1:4-4.3;
in the preparation of the modified 50-100nm ceramic membrane, the secondary activation solution comprises the following components in parts by weight: 4-6 parts of tetraethyl orthosilicate, 2-3 parts of aqueous solution of diallyl dimethyl ammonium chloride, 0.5-1 part of calcium propionate and 50-55 parts of ethanol;
in the preparation of the modified 50-100nm ceramic membrane, the content of diallyl dimethyl ammonium chloride in the aqueous solution of diallyl dimethyl ammonium chloride is 59-61%;
in the preparation of the modified 50-100nm ceramic membrane, the weight ratio of the ceramic membrane after secondary soaking to ammonia water is 1:3.5-4;
the nanofiltration is carried out, the clear liquid of the organic acid ammonium is led into a 200-300D nanofiltration membrane for nanofiltration, the clear phase obtained after the nanofiltration is finished is used as nanofiltration liquid, and the concentrated phase obtained by the nanofiltration is recycled;
the temperature during nanofiltration is 40-60 ℃ and the flow rate is 0.3-0.8m/s;
introducing the nanofiltration solution into an ion exchange system filled with strong acid gel type cation exchange resin to remove cations, and obtaining a cation removing solution after the removal of cations; the ion-exchanged resin is regenerated by hydrochloric acid or sulfuric acid with the mass fraction of 4.5-10.5% in a regeneration zone to obtain an organic acid ion-exchange regenerated liquid 1 containing ammonium chloride or ammonium sulfate with the mass fraction of 12-15%;
The temperature of the cation removal is 40-50 ℃, and the operating pressure is 0.10-0.20MPa;
the adsorption capacity of the strong acid gel type cation exchange resin is 1.9-2.1mol/L;
the organic acid ion exchange regenerated liquid 1 is recycled to the L-lysine production process after being refined, and is used for adjusting the ammonia concentration by an L-lysine ion exchange system or supplementing a nitrogen source in the L-lysine fermentation process.
Introducing the cation-removing liquid into an ion exchange system filled with gel-type weak base anion exchange resin to remove anions, and obtaining anion-removing liquid after the completion of anion removal; the ion-exchanged resin is subjected to ammonia water regeneration treatment with the mass fraction of 4.5-10.5% in a regeneration zone to obtain an organic acid ion-exchange regeneration liquid 2 containing 5-10% of ammonium chloride, ammonium sulfate and ammonium phosphate;
the organic acid ion exchange regenerated liquid 2 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The temperature of the product is 40-50 ℃ and the operating pressure is 0.12-0.20MPa.
The vacuum concentration and refining are carried out on the anion-removed liquid, and an organic acid product and an organic acid production waste liquid are obtained;
The vacuum concentration has a vacuum degree of 0.09-0.092MPa, a temperature of 70-75 ℃ and a time of 3-3.5h;
and (3) treating the organic acid production waste liquid, adding the organic acid production waste liquid into the organic acid ammonium clear liquid obtained by filtering the ceramic membrane, and recycling after nanofiltration, cation adsorption, anion adsorption, vacuum concentration and refining.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for jointly producing the organic acid and the L-lysine, disclosed by the invention, the ammonia is recovered from the production waste liquid after the L-lysine is produced, so that the utilization rate of the ammonia can be improved, the closed-loop production of the organic acid and the L-lysine is realized, and the energy consumption of raw materials, water and electricity and the like is reduced;
(2) The method for jointly producing the organic acid and the L-lysine can improve the yield and the output of the produced L-lysine;
(3) The method for jointly producing the organic acid and the L-lysine can improve the quality of the organic acid, the content of the organic acid in the prepared organic acid can reach 82.47-83.86g/dL, the content of residual sugar is 0g/dL, the content of chloride ions is 0mg/L, the content of sulfate radical is 0mg/L, and the chromaticity is 26.82-32.5apha;
(4) The method for jointly producing the organic acid and the L-lysine can improve the yield of the organic acid to 97.13-97.84 percent.
Drawings
FIG. 1 is a liquid chromatogram of an ammonium succinate pretreatment solution prepared in example 1;
FIG. 2 is a liquid chromatogram of the ammonium tartrate pretreatment liquid prepared in example 2;
FIG. 3 is a liquid chromatogram of the ammonium citrate pretreatment solution prepared in example 3;
fig. 4 is a liquid chromatogram of the ammonium itaconate pretreatment liquid prepared in example 4.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A method for the joint production of organic acid and L-lysine comprises the following steps:
l-lysine production
Adding a culture medium into a fermentation tank, and controlling the initial concentration of each component in the culture medium to be respectively as follows: glucose 50g/L, KH 2 PO 4 1.0g/L，MgSO 4 •7H 2 0 0.25g/L，（NH 4 ） 2 S0 4 40g/L，MnSO 4 0.05g/L，FeSO 4 0.05g/L，ZnC1 2 1mg/L，CuS0 4 Sterilizing the culture medium with 0.2mg/L, 100ug/L biotin and 1 mu g/L vitamin B, regulating pH of the culture medium to 6.5 with ammonia water, keeping constant, inoculating Corynebacterium glutamicum seed solution into the culture medium according to a ratio of 10%, introducing sterile air according to a volume ratio of ventilation rate per minute to the culture medium of 0.3:1, controlling the tank pressure of a fermentation tank to 0.1MPa during fermentation, feeding a carbon source and a nitrogen source, using ammonium chloride as the nitrogen source, culturing for 30h, regulating pH to 2.5 with sulfuric acid, filtering with a subsequent membrane, performing ion exchange, concentrating, crystallizing to obtain pure L-lysine and L-lysine crystallization mother liquor, and crystallizing the L-lysine to return to a production system Recycling, evaporating and deaminizing an dissociation collection liquid in ion exchange generated in the production of L-lysine, and concentrating and deaminizing the dissociation collection liquid in the ion exchange to obtain ammonia water with the mass fraction of 3% for adjusting the pH value by organic acid fermentation;
the nitrogen source in the production of the L-lysine is ammonium chloride generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of organic acid, and the carbon source is glucose.
2. Succinic acid production
(1) And (3) succinic acid fermentation: controlling the pH value to be 6.5-7.5 by adding ammonia water in a flowing way in the fermentation process of the succinic acid, and obtaining an ammonium succinate pretreatment liquid after the fermentation is finished;
the preparation method of the ammonia water comprises the steps of adding liquid ammonia into the ammonia water obtained in the step 1 of L-lysine production to adjust the concentration of the ammonia water to 5%;
the content of ammonium succinate in the ammonium succinate pretreatment liquid is 9g/dL, the gas chromatographic analysis is carried out on the ammonium succinate pretreatment liquid, the gas chromatographic chart is shown as the description of figure 1, and as can be seen from the figure 1, the optical purity of the ammonium succinate is 99.36%, the content of residual sugar is 0.27g/dL, the content of chloride ions is 447mg/L, the content of sulfate radical is 75mg/L, and the chromaticity is 47.4apha.
(2) And (3) ceramic membrane filtration: 450g (calculated by ammonium succinate) of ammonium succinate pretreatment liquid is introduced into a modified 50nm ceramic membrane for filtration, the temperature during filtration is controlled to be 75 ℃, the flow rate is 0.3m/s, the pressure is 4KPa, and the ammonium succinate clear liquid is obtained after the filtration.
The preparation method of the modified 50nm ceramic film comprises the following steps: placing a 50nm silicon nitride ceramic membrane into a primary activating solution for primary soaking, controlling the temperature at 85 ℃ during primary soaking for 1h, and obtaining a ceramic membrane after primary soaking after the primary soaking is finished; placing the ceramic membrane after primary soaking in secondary activating solution for secondary soaking, controlling the temperature at 65 ℃ for 50min when the secondary soaking is finished, obtaining the ceramic membrane after secondary soaking, placing the ceramic membrane after secondary soaking in ammonia water for tertiary soaking, controlling the temperature at-25 ℃ for 25min when the tertiary soaking is finished, placing the ceramic membrane in a sintering furnace after the tertiary soaking is finished, heating to 550 ℃ at the heating rate of 2 ℃/min, sintering for 1h at the temperature of 550 ℃, and naturally recovering to room temperature to obtain the modified 50nm ceramic membrane;
wherein the weight ratio of the 50nm silicon nitride ceramic film to the primary activating solution is 1:3.5;
the primary activating solution comprises the following components in parts by weight: 8 parts of sodium hydroxide, 2 parts of aluminum sulfate, 1 part of potassium sodium tartrate and 90 parts of deionized water;
wherein the weight ratio of the ceramic membrane after primary soaking to the secondary activating solution is 1:4;
the secondary activation liquid consists of the following components in parts by weight: 4 parts of tetraethyl orthosilicate, 2 parts of diallyl dimethyl ammonium chloride aqueous solution, 0.5 part of calcium propionate and 50 parts of ethanol;
The content of diallyl dimethyl ammonium chloride in the diallyl dimethyl ammonium chloride aqueous solution is 59%;
wherein the weight ratio of the ceramic membrane after the secondary soaking to the ammonia water is 1:3.5;
the content of ammonium succinate in the ammonium succinate clear liquid is 8.3g/dL, the content of residual sugar is 0.24g/dL, the content of chloride ions is 445mg/L, the content of sulfate radicals is 74mg/L, and the chromaticity is 38.1apha; wherein the mass of the ammonium succinate is 448.2g, and the yield is 99.60%.
(3) Nanofiltration: introducing the clear liquid of ammonium succinate into a 200D nanofiltration membrane for nanofiltration, and intercepting residual glucose, macromolecular proteins and pigments; controlling the temperature at 40 ℃ and the flow rate at 0.3m/s during nanofiltration, and taking the clear phase obtained after nanofiltration as nanofiltration liquid; after the concentrated phase obtained by nanofiltration is dialyzed by soft water to recover ammonium succinate, mixing the concentrated phase with ammonium succinate fermentation liquor obtained by the succinic acid fermentation in the step (1) for continuous recycling;
the content of ammonium succinate in the nanofiltration solution is 8.25g/dL, the content of residual sugar is 0.22g/dL, the content of chloride ions is 445mg/L, the content of sulfate radicals is 21mg/L, and the chromaticity is 28.7apha; wherein the mass of the ammonium succinate is 443.5g, and the yield is 98.56%.
(4) Adsorption of cations: introducing the nanofiltration solution into an ion exchange system filled with strong acid gel type cation exchange resin for cation removal, controlling the temperature at 40 ℃ and the operating pressure at 0.10MPa when the cation removal is performed, and obtaining the cation removal solution after the cation removal is finished; the ion-exchanged resin is subjected to hydrochloric acid regeneration treatment with the mass fraction of 4.5% in a regeneration zone to obtain an organic acid ion-exchange regenerated liquid 1 containing ammonium chloride with the mass fraction of 12%;
The adsorption capacity of the strong acid gel type cation exchange resin is 1.9mol/L;
the organic acid ion exchange regenerated liquid 1 is recycled to the L-lysine production process after being refined and used for regulating the ammonia concentration by an L-lysine ion exchange system.
The content of succinic acid in the decationizing liquid is 8.22g/dL, the content of residual sugar is 0.021g/dL, the content of chloride ions is 445mg/L, the content of sulfate radicals is 21mg/L, and the chromaticity is 12.5apha; the mass of succinic acid was 443.1g, and the yield was 98.47%.
(5) Adsorption of anions: introducing the deionized water into an ion exchange system filled with gel-type weak base anion exchange resin to perform anion removal, controlling the temperature at 40 ℃ and the operating pressure at 0.12MPa when the anion removal is performed, and obtaining the deionized water after the anion removal is finished; the ion-exchanged resin is subjected to regeneration treatment of ammonia water with the mass fraction of 4.5% in a regeneration zone to obtain an organic acid ion-exchange regeneration liquid 2 containing 5% of ammonium chloride, ammonium sulfate and ammonium phosphate;
the organic acid ion exchange regenerated liquid 2 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The content of succinic acid in the de-anion liquid is 8.21g/dL, the content of residual sugar is 0.019g/dL, the content of chloride ions is 0mg/L, the content of sulfate radicals is 0mg/L, and the chromaticity is 7.2apha; wherein the mass of the succinic acid is 441.2g, and the yield is 98.04%.
(6) Vacuum concentration and refining: vacuum concentrating and refining the anion-removed liquid, controlling the vacuum degree at 0.09MPa, the temperature at 70 ℃ and the time at 3h during vacuum concentration to obtain a succinic acid product and succinic acid production waste liquid;
the succinic acid product contains 82.47g/dL of succinic acid, 0g/dL of residual sugar, 0mg/L of chloride ions, 0mg/L of sulfate radicals and 32.5apha of chromaticity; wherein the mass of the succinic acid is 439.2g, and the yield is 97.60%.
(7) Treatment of succinic acid production waste liquid: and adding the succinic acid production waste liquid into the ammonium succinate clear liquid obtained by filtering the ceramic membrane, and recycling the ammonium succinate clear liquid after nanofiltration, cation adsorption, anion adsorption, vacuum concentration and refining, thereby improving the succinic acid yield.
Example 2
A method for the joint production of organic acid and L-lysine comprises the following steps:
l-lysine production
Adding a culture medium into a fermentation tank, and controlling the initial concentration of each component in the culture medium to be respectively as follows: glucose 51g/L, KH 2 PO 4 1.1g/L，MgSO 4 •7H 2 0 0.27g/L，（NH 4 ） 2 S0 4 41g/L，MnSO 4 0.052g/L，FeSO 4 0.055g/L，ZnC1 2 1.1mg/L，CuS0 4 Sterilizing the culture medium with 0.22mg/L, 110ug/L biotin and 1 mug/L vitamin B, regulating the pH of the culture medium to 6.8 by ammonia water, keeping the pH constant, inoculating a corynebacterium glutamicum seed solution into the culture medium according to the proportion of 12%, then introducing sterile air according to the volume ratio of ventilation quantity per minute to the culture medium of 0.3:1, controlling the tank pressure of a fermentation tank to be 0.13MPa in the fermentation process, feeding a carbon source, a nitrogen source and ammonium sulfate for use, culturing for 35 hours, regulating the pH to 3 by sulfuric acid, filtering by a subsequent membrane, carrying out ion exchange, concentrating, crystallizing to obtain pure L-lysine and L-lysine crystallization mother liquor, recycling the L-lysine crystallization mother liquor back to a production system, evaporating and deaminizing a release liquid in the ion exchange generated by L-lysine production, wherein the mass fraction of the release liquid obtained after concentration deaminizing in the ion exchange is 3.5% ammonia water for use in organic acid fermentation pH regulation;
The nitrogen source in the production of the L-lysine is ammonium sulfate generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of organic acid, and the carbon source is glucose.
2. Tartaric acid production
(1) Fermenting ammonium tartrate: controlling the pH value to be 6.5-7.5 by adding ammonia water in a flowing way in the fermentation process of tartaric acid, and obtaining ammonium tartrate pretreatment liquid after fermentation;
the preparation method of the ammonia water comprises the steps of adding liquid ammonia into the ammonia water obtained in the step 1 of L-lysine production to adjust the concentration of the ammonia water to 5%;
the content of ammonium tartrate in the ammonium tartrate pretreatment liquid is 9.7g/dL, the gas chromatographic analysis is carried out on the ammonium tartrate pretreatment liquid, the gas chromatographic chart is shown in figure 2, and as can be seen from figure 2, the optical purity of the ammonium tartrate is 100%, the content of residual sugar is 0.31g/dL, the content of chloride ions is 425mg/L, the content of sulfate radical is 70mg/L, and the chromaticity is 51.2apha.
(2) And (3) ceramic membrane filtration: 450g (calculated by ammonium tartrate) of ammonium tartrate pretreatment solution is introduced into a modified 60nm ceramic membrane for filtration, the temperature during filtration is controlled to be 77 ℃, the flow rate is 0.35m/s, the pressure is 4.2KPa, and the ammonium tartrate clear liquid is obtained after the filtration.
The preparation method of the modified 60nm ceramic film comprises the following steps: placing a 60nm silicon nitride ceramic membrane into a primary activating solution for primary soaking, controlling the temperature at 87 ℃ during primary soaking for 1.1h, and obtaining a ceramic membrane after primary soaking after the primary soaking is finished; placing the ceramic membrane after primary soaking in secondary activating solution for secondary soaking, controlling the temperature at 67 ℃ for 52min during secondary soaking, obtaining the ceramic membrane after secondary soaking after finishing secondary soaking, placing the ceramic membrane after secondary soaking in ammonia water for tertiary soaking, controlling the temperature at-22 ℃ for 26min during tertiary soaking, placing the ceramic membrane in a sintering furnace after finishing tertiary soaking, heating to 560 ℃ at the heating rate of 2.1 ℃/min, sintering for 1.1h at 560 ℃, and naturally recovering to room temperature to obtain the modified 60nm ceramic membrane;
wherein the weight ratio of the 60nm silicon nitride ceramic film to the primary activating solution is 1:3.6;
the primary activating solution comprises the following components in parts by weight: 9 parts of sodium hydroxide, 2.4 parts of aluminum sulfate, 1.2 parts of potassium sodium tartrate and 92 parts of deionized water;
wherein the weight ratio of the ceramic membrane after primary soaking to the secondary activating solution is 1:4.2;
the secondary activation liquid consists of the following components in parts by weight: 5 parts of tetraethyl orthosilicate, 2.3 parts of diallyl dimethyl ammonium chloride aqueous solution, 0.6 part of calcium propionate and 52 parts of ethanol;
The content of diallyl dimethyl ammonium chloride in the diallyl dimethyl ammonium chloride aqueous solution is 59%;
wherein the weight ratio of the ceramic membrane after the secondary soaking to the ammonia water is 1:3.7;
the content of ammonium tartrate in the ammonium tartrate clear liquid is 8.8g/dL, the content of residual sugar is 0.29g/dL, the content of chloride ions is 425mg/L, the content of sulfate radicals is 68mg/L, and the chromaticity is 40.5apha; wherein, the mass of ammonium tartrate is 449.1g, and the yield is 99.80%.
(3) Nanofiltration: introducing the ammonium tartrate clear liquid into a 220D nanofiltration membrane for nanofiltration, and intercepting residual glucose, macromolecular proteins and pigments; controlling the temperature at 45 ℃ and the flow rate at 0.4m/s during nanofiltration, and taking the clear phase obtained after nanofiltration as nanofiltration liquid; after the concentrated phase obtained by nanofiltration is dialyzed by soft water to recover ammonium tartrate, mixing the concentrated phase with ammonium tartrate fermentation liquor obtained by fermenting the tartaric acid in the step (1) for continuous recycling;
the content of ammonium tartrate in the nanofiltration solution is 8.4g/dL, the content of residual sugar is 0.25g/dL, the content of chloride ions is 414mg/L, the content of sulfate radicals is 22mg/L, and the chromaticity is 27.6apha; wherein, the mass of the ammonium tartrate is 444.2g, and the yield is 98.71%.
(4) Adsorption of cations: introducing the nanofiltration solution into an ion exchange system filled with strong acid gel type cation exchange resin to remove cations, controlling the temperature at 45 ℃ and the operating pressure at 0.12MPa; the cation removal is finished to obtain cation removal liquid; the ion-exchanged resin is subjected to sulfuric acid regeneration treatment with the mass fraction of 6% in a regeneration zone to obtain an organic acid ion-exchange regenerated liquid 1 containing ammonium sulfate with the mass fraction of 13%;
The adsorption capacity of the strong acid gel type cation exchange resin is 1.95mol/L;
the organic acid ion exchange regenerated liquid 1 is recycled to the L-lysine production process after being refined and used for regulating the ammonia concentration by an L-lysine ion exchange system.
The content of tartaric acid in the decationizing liquid is 8.32g/dL, the content of residual sugar is 0.022g/dL, the content of chloride ions is 401mg/L, the content of sulfate radicals is 20mg/L, and the chromaticity is 11.5apha; wherein the mass of tartaric acid is 443.8g, and the yield is 98.62%.
(5) Adsorption of anions: introducing the deionized water into an ion exchange system filled with gel-type weak base anion exchange resin to perform anion removal, controlling the temperature at 42 ℃ and the operating pressure at 0.14MPa when the anion removal is performed, and obtaining the deionized water after the anion removal is finished; the ion-exchanged resin is subjected to ammonia water regeneration treatment with the mass fraction of 6% in a regeneration zone to obtain an organic acid ion-exchange regeneration liquid 2 containing ammonium chloride, ammonium sulfate and ammonium phosphate with the mass fraction of 7%;
the organic acid ion exchange regenerated liquid 2 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The content of tartaric acid in the deionized liquid is 8.3g/dL, the content of residual sugar is 0.021g/dL, the content of chloride ions is 0mg/L, the content of sulfate radicals is 0mg/L, and the chromaticity is 6.8apha; wherein the mass of tartaric acid is 440.5g, and the yield is 97.89%.
(6) Vacuum concentration and refining: vacuum concentrating and refining the deionized liquid, wherein the vacuum degree during vacuum concentration is controlled to be 0.091MPa, the temperature is 72 ℃ and the time is 3.2h, so as to obtain tartaric acid products and tartaric acid production waste liquid;
the tartaric acid product has the tartaric acid content of 83.54g/dL, the residual sugar content of 0g/dL, the chloride ion content of 0mg/L, the sulfate radical content of 0mg/L and the chromaticity of 30.2apha; wherein the mass of tartaric acid is 437.1g, and the yield is 97.13%.
(7) Treatment of tartaric acid production waste liquid: and adding the waste liquid from tartaric acid production into the ammonium tartrate clear liquid obtained by filtering the ceramic membrane, and recycling after nanofiltration, cation adsorption, anion adsorption, vacuum concentration and refining, thereby improving the tartaric acid yield.
Example 3
A method for the joint production of organic acid and L-lysine comprises the following steps:
l-lysine production
Adding a culture medium into a fermentation tank, and controlling the initial concentration of each component in the culture medium to be respectively as follows: glucose 51g/L, KH 2 PO 4 1.2g/L，MgSO 4 •7H 2 0 0.28g/L，（NH 4 ） 2 S0 4 42g/L，MnSO 4 0.058g/L，FeSO 4 0.06g/L，ZnC1 2 1.2mg/L，CuS0 4 Sterilizing the culture medium with 0.28mg/L, 120ug/L biotin and 210 ug/L vitamin B, regulating the pH of the culture medium to 7.2 by ammonia water, keeping the pH constant, inoculating Corynebacterium glutamicum seed solution into the culture medium according to the proportion of 17%, introducing sterile air according to the volume ratio of ventilation quantity per minute to the culture medium of 0.3:1, controlling the tank pressure of a fermentation tank to 0.17MPa in the fermentation process, feeding a carbon source and a nitrogen source, using ammonium chloride as the nitrogen source, culturing for 42h, regulating the pH to 4 by sulfuric acid, filtering by a subsequent membrane, performing ion exchange, concentrating, crystallizing to obtain pure L-lysine and L-lysine crystallization mother liquor, recycling the L-lysine crystallization mother liquor back to a production system, evaporating and deaminizing the dissociation collection in the ion exchange generated by L-lysine production, wherein the mass fraction of the dissociation collection in the ion exchange is 4.5% ammonia water obtained after concentration deaminizing is used for organic acid fermentation pH regulation;
The nitrogen source in the production of the L-lysine is ammonium chloride generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of organic acid, and the carbon source is glucose.
2. Citric acid production
(1) Ammonium citrate fermentation: controlling the pH value to be 6.5-7.5 by adding ammonia water in a flowing way in the fermentation process of the citric acid, and obtaining ammonium citrate pretreatment liquid after the fermentation is finished;
the preparation method of the ammonia water comprises the steps of adding liquid ammonia into the ammonia water obtained in the step 1 of L-lysine production to adjust the concentration of the ammonia water to 15%;
the content of ammonium citrate in the ammonium citrate pretreatment liquid is 9.5g/dL, the ammonium citrate pretreatment liquid is subjected to gas chromatography analysis, the gas chromatography is shown in figure 3, and as can be seen from figure 3, the optical purity of the ammonium citrate is 99.86%, the content of residual sugar is 0.23g/dL, the content of chloride ions is 420mg/L, the content of sulfate radical is 84mg/L, and the chromaticity is 52.3apha.
(2) And (3) ceramic membrane filtration: 450g (calculated by ammonium citrate) of ammonium citrate pretreatment solution is introduced into a modified 80nm ceramic membrane for filtration, the temperature during filtration is controlled to be 78 ℃, the flow rate is 0.45m/s, the pressure is 4.8KPa, and the ammonium citrate clear liquid is obtained after the filtration.
The preparation method of the modified 80nm ceramic film comprises the following steps: placing the 80nm silicon nitride ceramic membrane into a primary activating solution for primary soaking, controlling the temperature at 88 ℃ during primary soaking for 1.1h, and obtaining the ceramic membrane after primary soaking after the primary soaking is finished; placing the ceramic membrane after primary soaking in secondary activating solution for secondary soaking, controlling the temperature at 68 ℃ for 54min when the secondary soaking is finished, obtaining the ceramic membrane after secondary soaking, placing the ceramic membrane after secondary soaking in ammonia water for tertiary soaking, controlling the temperature at-23 ℃ for 28min when the tertiary soaking is finished, placing the ceramic membrane in a sintering furnace after the tertiary soaking is finished, heating to 570 ℃ at the heating rate of 2.3 ℃/min, sintering for 1.1h at 570 ℃, and naturally recovering to room temperature to obtain the modified 80nm ceramic membrane;
wherein the weight ratio of the 80nm silicon nitride ceramic film to the primary activating solution is 1:3.8;
the primary activating solution comprises the following components in parts by weight: 9 parts of sodium hydroxide, 2.6 parts of aluminum sulfate, 1.4 parts of potassium sodium tartrate and 94 parts of deionized water;
wherein the weight ratio of the ceramic membrane after primary soaking to the secondary activating solution is 1:4.2;
the secondary activation liquid consists of the following components in parts by weight: 5 parts of tetraethyl orthosilicate, 2.8 parts of an aqueous solution of diallyl dimethyl ammonium chloride, 0.8 part of calcium propionate and 54 parts of ethanol;
The content of diallyl dimethyl ammonium chloride in the diallyl dimethyl ammonium chloride aqueous solution is 60%;
wherein the weight ratio of the ceramic membrane after the secondary soaking to the ammonia water is 1:3.8;
the content of ammonium citrate in the ammonium citrate clear liquid is 8.8g/dL, the content of residual sugar is 0.21g/dL, the content of chloride ions is 417mg/L, the content of sulfate radicals is 78mg/L, and the chromaticity is 40.2apha; wherein, the mass of the ammonium citrate is 447.8g, and the yield is 99.51%.
(3) Nanofiltration: introducing the ammonium citrate clear solution into a 280D nanofiltration membrane for nanofiltration, and intercepting residual glucose, macromolecular proteins and pigments; controlling the temperature at 55 ℃ and the flow rate at 0.7m/s during nanofiltration, and taking the clear phase obtained after nanofiltration as nanofiltration liquid; after the concentrated phase obtained by nanofiltration is dialyzed by soft water to recover ammonium citrate, mixing the concentrated phase with ammonium citrate fermentation liquor obtained by fermenting the ammonium citrate in the step (1) for continuous recycling;
the content of ammonium citrate in the nanofiltration solution is 8.48g/dL, the content of residual sugar is 0.2g/dL, the content of chloride ions is 417mg/L, the content of sulfate radicals is 22mg/L, and the chromaticity is 25.2apha; wherein, the mass of the ammonium citrate is 445.2g, and the yield is 98.93%.
(4) Adsorption of cations: introducing the nanofiltration solution into an ion exchange system filled with strong acid gel type cation exchange resin for cation removal, controlling the temperature at 48 ℃ and the operating pressure at 0.18MPa when the cation removal is performed, and obtaining the cation removal solution after the cation removal is finished; the ion-exchanged resin is subjected to hydrochloric acid regeneration treatment with the mass fraction of 9% in a regeneration zone to obtain an organic acid ion-exchange regeneration liquid 1 containing ammonium chloride with the mass fraction of 14%;
The organic acid ion exchange regenerated liquid 1 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The adsorption capacity of the strong acid gel type cation exchange resin is 2mol/L.
The content of citric acid in the decationizing liquid is 8.36g/dL, the content of residual sugar is 0.031g/dL, the content of chloride ions is 416mg/L, the content of sulfate radicals is 21mg/L, and the chromaticity is 13.7apha; wherein, the mass of the citric acid is 442.8g, and the yield is 98.40%.
(5) Adsorption of anions: introducing the deionized water into an ion exchange system filled with gel-type weak base anion exchange resin to perform anion removal, controlling the temperature at 48 ℃ and the operating pressure at 0.18MPa when the anion removal is performed, and obtaining the deionized water after the anion removal is finished; the ion-exchanged resin is subjected to regeneration treatment of ammonia water with the mass fraction of 9% in a regeneration zone to obtain an organic acid ion-exchange regeneration liquid 2 containing ammonium chloride, ammonium sulfate and ammonium phosphate with the mass fraction of 10%;
the organic acid ion exchange regenerated liquid 2 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The content of citric acid in the deionized liquid is 8.3g/dL, the content of residual sugar is 0.018g/dL, the content of chloride ions is 0mg/L, the content of sulfate radicals is 0mg/L, and the chromaticity is 7.5apha; wherein, the mass of the citric acid is 441.9g, and the yield is 98.20%.
(6) Vacuum concentration and refining: vacuum concentrating and refining the deionized liquid, wherein the vacuum degree during vacuum concentration is controlled to be 0.091MPa, the temperature is 74 ℃ and the time is 3.4 hours, so as to obtain a citric acid product and citric acid organic waste liquid;
the content of citric acid in the citric acid product is 83.86g/dL, the content of residual sugar is 0g/dL, the content of chloride ions is 0mg/L, the content of sulfate radicals is 0mg/L, and the chromaticity is 26.82apha; wherein, the mass of the citric acid is 440.3g, and the yield is 97.84%.
(7) Treatment of citric acid production waste liquid: and adding the citric acid production waste liquid into the ammonium citrate clear liquid obtained by filtering the ceramic membrane, and recycling after nanofiltration, cation adsorption, anion adsorption, vacuum concentration and refining, thereby improving the yield of the citric acid.
Example 4
A method for the joint production of organic acid and L-lysine comprises the following steps:
l-lysine production
Adding a culture medium into a fermentation tank, and controlling the initial concentration of each component in the culture medium to be respectively as follows: glucose 52g/L, KH 2 PO 4 1.2g/L，MgSO 4 •7H 2 0 0.3g/L，（NH 4 ） 2 S0 4 43g/L，MnSO 4 0.06g/L，FeSO 4 0.07g/L，ZnC1 2 1.3mg/L，CuS0 4 Sterilizing the culture medium with 0.3mg/L, 130ug/L biotin and 220 ug/L vitamin B, regulating the pH of the culture medium to 7.5 by ammonia water, keeping the pH constant, inoculating Corynebacterium glutamicum seed solution into the culture medium according to the proportion of 20%, introducing sterile air according to the volume ratio of ventilation quantity per minute to the culture medium of 0.3:1, controlling the tank pressure of a fermentation tank to 0.2MPa in the fermentation process, feeding a carbon source and a nitrogen source, using ammonium sulfate as the nitrogen source, culturing for 48 hours, regulating the pH to 4.5 by sulfuric acid, filtering by a subsequent membrane, performing ion exchange, concentrating, crystallizing to obtain pure L-lysine and L-lysine crystallization mother liquor, recycling the L-lysine crystallization mother liquor to a production system, evaporating and deaminizing the disaggregation liquid in the ion exchange generated by the L-lysine production, and concentrating the disaggregation liquid in the ion exchange to obtain ammonia water with the mass fraction of 5% for regulating the pH by fermentation of organic acid;
The nitrogen source in the production of the L-lysine is ammonium sulfate generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of organic acid, and the carbon source is glucose.
2. Itaconic acid production
(1) Fermenting the ammonium itaconate: controlling the pH value to be 6.5-7.5 by adding ammonia water in a flowing way in the fermentation process of itaconic acid, and obtaining an ammonium itaconate pretreatment liquid after the fermentation is finished;
the preparation method of the ammonia water comprises the steps of adding liquid ammonia into the ammonia water obtained in the step 1 of L-lysine production to adjust the concentration of the ammonia water to 5%;
the content of the ammonium itaconate in the ammonium itaconate pretreatment liquid is 9.8g/dL, the ammonium itaconate pretreatment liquid is subjected to gas chromatographic analysis, the gas chromatographic chart is shown as a graph in fig. 4, and as can be seen from fig. 4, the optical purity of the ammonium itaconate is 100%, the content of residual sugar is 0.25g/dL, the content of chloride ions is 435mg/L, the content of sulfate radicals is 80mg/L, and the chromaticity is 49.1apha.
(2) And (3) ceramic membrane filtration: 450g (calculated by ammonium itaconate) of ammonium itaconate pretreatment liquid is introduced into a modified 100nm ceramic membrane for filtration, the temperature during filtration is controlled to be 80 ℃, the flow rate is 0.5m/s, the pressure is 5KPa, and the ammonium itaconate clear liquid is obtained after the filtration is finished.
The preparation method of the modified 100nm ceramic film comprises the following steps: placing a 100nm silicon nitride ceramic membrane into a primary activating solution for primary soaking, controlling the temperature at 90 ℃ during primary soaking for 1.2 hours, and obtaining a ceramic membrane after primary soaking after the primary soaking is finished; placing the ceramic membrane after primary soaking in secondary activating solution for secondary soaking, controlling the temperature at 70 ℃ and the time at 55min when the secondary soaking is finished, obtaining the ceramic membrane after secondary soaking, placing the ceramic membrane after secondary soaking in ammonia water for tertiary soaking, controlling the temperature at-20 ℃ and the time at 30min when the tertiary soaking is finished, placing the ceramic membrane in a sintering furnace, heating to 580 ℃ at the heating rate of 2.5 ℃/min after the tertiary soaking is finished, sintering for 1.2h at 580 ℃, and naturally recovering to room temperature to obtain the modified 100nm ceramic membrane;
wherein the weight ratio of the 100nm silicon nitride ceramic film to the primary activating solution is 1:4;
the primary activating solution comprises the following components in parts by weight: 10 parts of sodium hydroxide, 3 parts of aluminum sulfate, 1.5 parts of potassium sodium tartrate and 95 parts of deionized water;
wherein the weight ratio of the ceramic membrane after primary soaking to the secondary activating solution is 1:4.3;
the secondary activation liquid consists of the following components in parts by weight: 6 parts of tetraethyl orthosilicate, 3 parts of diallyl dimethyl ammonium chloride aqueous solution, 1 part of calcium propionate and 55 parts of ethanol;
The content of diallyl dimethyl ammonium chloride in the diallyl dimethyl ammonium chloride aqueous solution is 61%;
wherein the weight ratio of the ceramic membrane after the secondary soaking to the ammonia water is 1:4;
the content of the itaconic acid ammonium in the clear solution of the itaconic acid ammonium is 8.3g/dL, the content of residual sugar is 0.24g/dL, the content of chloride ions is 433mg/L, the content of sulfate radicals is 78mg/L, and the chromaticity is 41.7apha; wherein, the mass of the ammonium itaconate is 449.3g, and the yield is 99.84%.
(3) Nanofiltration: introducing the clear solution of the ammonium itaconate into a 300D nanofiltration membrane for nanofiltration, and intercepting residual glucose, macromolecular proteins and pigments; controlling the temperature at 60 ℃ and the flow rate at 0.8m/s during nanofiltration, and taking the clear phase obtained after nanofiltration as nanofiltration liquid; after the concentrated phase obtained by nanofiltration is dialyzed by soft water to recover the ammonium itaconate, mixing the concentrated phase with the ammonium itaconate fermentation liquid after the ammonium itaconate fermentation in the step (1) is completed, and continuously recycling the mixture;
the content of the ammonium itaconate in the nanofiltration solution is 8.27g/dL, the content of residual sugar is 0.22g/dL, the content of chloride ions is 433mg/L, the content of sulfate radicals is 25mg/L, and the chromaticity is 30.4apha; wherein, the mass of the ammonium itaconate is 442.4g, and the yield is 98.31%.
(4) Adsorption of cations: introducing the nanofiltration solution into an ion exchange system filled with strong acid gel type cation exchange resin for cation removal, controlling the temperature at 50 ℃ and the operating pressure at 0.20MPa when the cation removal is performed, and obtaining the cation removal solution after the cation removal is finished; the ion-exchanged resin is subjected to sulfuric acid regeneration treatment with the mass fraction of 10.5% in a regeneration zone to obtain an organic acid ion-exchange regenerated liquid 1 containing 15% of ammonium sulfate;
The organic acid ion exchange regenerated liquid 1 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The adsorption quantity of the strong acid gel type cation exchange resin is 2.1mol/L.
The content of the itaconic acid in the decationizing liquid is 8.23g/dL, the content of residual sugar is 0.021g/dL, the content of chloride ions is 433mg/L, the content of sulfate radicals is 22mg/L, and the chromaticity is 11.9apha; wherein, the mass of the itaconic acid is 441.5g, and the yield is 98.11%.
(5) Adsorption of anions: introducing the deionized water into an ion exchange system filled with gel-type weak base anion exchange resin to perform anion removal, controlling the temperature at 50 ℃ and the operating pressure at 0.20MPa when the anion removal is performed, and obtaining the deionized water after the anion removal is finished; the ion-exchanged resin is subjected to ammonia water regeneration treatment with the mass fraction of 10.5% in a regeneration zone to obtain an organic acid ion exchange regeneration liquid 2 containing ammonium chloride, ammonium sulfate and ammonium phosphate with the mass fraction of 10%;
the organic acid ion exchange regenerated liquid 2 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process.
The content of the itaconic acid in the anion removing liquid is 8.2g/dL, the content of residual sugar is 0.02g/dL, the content of chloride ions is 0mg/L, the content of sulfate radicals is 0mg/L, and the chromaticity is 6.4apha; wherein, the mass of itaconic acid is 440.3g, and the yield is 97.84%.
(6) Vacuum concentration and refining: vacuum concentrating and refining the deionized liquid, wherein the vacuum degree during vacuum concentration is controlled to be 0.092MPa, the temperature is 75 ℃, and the time is 3.5 hours, so that itaconic acid products and itaconic acid production waste liquid are obtained;
the itaconic acid product has the content of itaconic acid of 83.04g/dL, the content of residual sugar of 0g/dL, the content of chloride ions of 0mg/L, the content of sulfate radicals of 0mg/L and the chromaticity of 29.5apha; wherein, the mass of itaconic acid is 438.7g, and the yield is 97.49%.
(7) Treatment of waste liquid from itaconic acid production: and adding itaconic acid production waste liquid into the ammonium itaconate clear liquid obtained by filtering the ceramic membrane, and recycling after nanofiltration, cation adsorption, anion adsorption, vacuum concentration and refining.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for the joint production of organic acid and L-lysine, which is characterized by comprising the following steps: l-lysine production and organic acid production;
the method comprises the steps of L-lysine production, adding a culture medium into a fermentation tank, sterilizing the culture medium, regulating the pH of the culture medium to 6.5-7.5 by using ammonia water, keeping the pH constant, inoculating corynebacterium glutamicum seed liquid into the culture medium according to the proportion of 10-20%, introducing sterile air according to the volume ratio of ventilation quantity to the culture medium of 0.3:1, controlling the tank pressure of the fermentation tank to be 0.1-0.2MPa in the fermentation process, feeding a carbon source and a nitrogen source, using ammonium sulfate or ammonium chloride as the nitrogen source, culturing for 30-48h, regulating the pH to 2.5-4.5 by using sulfuric acid, filtering by using a subsequent membrane, carrying out ion exchange, concentrating, crystallizing to obtain pure L-lysine and L-lysine crystallization mother liquor, recycling the L-lysine crystallization mother liquor in the production system, evaporating and deaminizing the solution in the ion exchange generated in the production of L-lysine, and concentrating and deaminizing the solution in the ion exchange solution for regulating the pH by using ammonia water for organic acid fermentation;
the organic acid production consists of the following steps: fermenting organic acid, filtering by a ceramic membrane, nanofiltration, adsorbing cations, adsorbing anions, concentrating and refining in vacuum, and treating waste liquid generated in the production of the organic acid;
The pH value of the organic acid fermentation is controlled to be 6.5-7.5 by adding ammonia water in a flowing way in the fermentation process of the organic acid, and the organic acid ammonium pretreatment liquid is obtained after the fermentation is finished;
in the organic acid fermentation, the preparation method of the ammonia water comprises the steps of adding liquid ammonia into the ammonia water obtained in the L-lysine production to adjust the concentration of the ammonia water to 5-15%;
the ceramic membrane is used for filtering, the organic acid ammonium pretreatment liquid is introduced into a modified 50-100nm ceramic membrane for filtering, and the organic acid ammonium clear liquid is obtained after the filtering is finished;
the preparation method of the modified 50-100nm ceramic film comprises the following steps: placing a silicon nitride ceramic film with the thickness of 50-100nm into a primary activating solution for primary soaking, controlling the temperature at 85-90 ℃ for 1-1.2h during primary soaking, and obtaining a ceramic film after primary soaking after the primary soaking is finished; placing the ceramic membrane after primary soaking in secondary activating solution for secondary soaking, controlling the temperature at 65-70 ℃ for 50-55min when the secondary soaking is finished, obtaining the ceramic membrane after secondary soaking, placing the ceramic membrane after secondary soaking in ammonia water for tertiary soaking, controlling the temperature at-25 ℃ to-20 ℃ when the tertiary soaking is finished, and controlling the time at 25-30min, placing the ceramic membrane in a sintering furnace after the tertiary soaking is finished, heating to 550-580 ℃ at the heating rate of 2-2.5 ℃/min, sintering for 1-1.2h at 550-580 ℃, and naturally recovering to room temperature to obtain the modified ceramic membrane with the wavelength of 50-100 nm;
In the preparation of the modified 50-100nm ceramic film, the weight ratio of the 50-100nm silicon nitride ceramic film to the primary activating solution is 1:3.5-4;
in the preparation of the modified 50-100nm ceramic membrane, the primary activating solution comprises the following components in parts by weight: 8-10 parts of sodium hydroxide, 2-3 parts of aluminum sulfate, 1-1.5 parts of potassium sodium tartrate and 90-95 parts of deionized water;
in the preparation of the modified 50-100nm ceramic membrane, the weight ratio of the ceramic membrane after primary soaking to the secondary activating solution is 1:4-4.3;
in the preparation of the modified 50-100nm ceramic membrane, the secondary activation solution comprises the following components in parts by weight: 4-6 parts of tetraethyl orthosilicate, 2-3 parts of aqueous solution of diallyl dimethyl ammonium chloride, 0.5-1 part of calcium propionate and 50-55 parts of ethanol;
in the preparation of the modified 50-100nm ceramic membrane, the content of diallyl dimethyl ammonium chloride in the aqueous solution of diallyl dimethyl ammonium chloride is 59-61%;
in the preparation of the modified 50-100nm ceramic membrane, the weight ratio of the ceramic membrane after secondary soaking to ammonia water is 1:3.5-4;
introducing the nanofiltration solution into an ion exchange system filled with strong acid gel type cation exchange resin to remove cations, and obtaining a cation removing solution after the removal of cations; the ion-exchanged resin is regenerated by hydrochloric acid or sulfuric acid with the mass fraction of 4.5-10.5% in a regeneration zone to obtain an organic acid ion exchange regeneration liquid 1 containing 12-15% of ammonium chloride or ammonium sulfate;
The temperature of the cation removal is 40-50 ℃, and the operating pressure is 0.10-0.20MPa;
the adsorption capacity of the strong acid gel type cation exchange resin is 1.9-2.1mol/L;
the organic acid ion exchange regenerated liquid 1 is recycled to the L-lysine production process after being refined, and is used for adjusting the ammonia concentration by an L-lysine ion exchange system or supplementing a nitrogen source in the L-lysine fermentation process;
introducing the cation-removing liquid into an ion exchange system filled with gel-type weak base anion exchange resin to remove anions, and obtaining anion-removing liquid after the completion of anion removal; the ion-exchanged resin is subjected to ammonia water regeneration treatment with the mass fraction of 4.5-10.5% in a regeneration zone to obtain an organic acid ion-exchange regeneration liquid 2 containing 5-10% of ammonium chloride, ammonium sulfate and ammonium phosphate;
the organic acid ion exchange regenerated liquid 2 is recycled to the L-lysine production process after being refined and used for supplementing nitrogen sources in the L-lysine fermentation process;
the temperature of the product is 40-50 ℃ and the operating pressure is 0.12-0.20MPa.
2. The method for the joint production of an organic acid and L-lysine according to claim 1, wherein the initial concentrations of the respective components of the medium in the production of L-lysine are respectively: glucose 50-52g/L KH 2 PO 4 1-1.2g/L，MgSO 4 •7H 2 0 0.25-0.3g/L，（NH 4 ） 2 S0 4 40-43g/L，MnSO 4 0.05-0.06g/L，FeSO 4 0.05-0.07g/L，ZnC1 2 1-1.3mg/L，CuS0 4 0.2-0.3mg/L, biotin 100-130ug/L, vitamin B1 200-220 ug/L.
3. The method for the combined production of an organic acid and L-lysine according to claim 1, wherein the nitrogen source in the production of L-lysine is ammonium sulfate or ammonium chloride generated in the regeneration production process of cation exchange resin and anion exchange resin which adsorb cations and anions in the production of the organic acid, and the carbon source is glucose.
4. The method for co-production of an organic acid and L-lysine according to claim 1, wherein the ceramic membrane filtration is performed at a temperature of 60 to 80 ℃, a flow rate of 0.3 to 0.5m/s, and a pressure of 4 to 5KPa.
5. The method for the joint production of organic acid and L-lysine according to claim 1, wherein the nanofiltration is carried out by introducing the clear liquid of the organic acid ammonium into a 200-300D nanofiltration membrane for nanofiltration, taking the clear phase obtained after the nanofiltration as nanofiltration liquid, and recycling the concentrated phase obtained by the nanofiltration;
the temperature during nanofiltration is 40-60 ℃ and the flow rate is 0.3-0.8m/s.
6. The method for the combined production of organic acid and L-lysine according to claim 1, wherein the vacuum concentration and refining are carried out on the anion-removed liquid to obtain an organic acid product and an organic acid production waste liquid;
The vacuum concentration has a vacuum degree of 0.09-0.092MPa, a temperature of 70-75 ℃ and a time of 3-3.5h;
and (3) treating the organic acid production waste liquid, adding the organic acid production waste liquid into the organic acid ammonium clear liquid obtained by filtering the ceramic membrane, and recycling after nanofiltration, cation adsorption, anion adsorption, vacuum concentration and refining.
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